KR20160121045A - High density polyethylene copolymer for blow molding - Google Patents

Abstract

The present invention relates to an ethylene / alpha-olefin copolymer and the ethylene / alpha-olefin copolymer according to the present invention has a high Mp value and excellent die swelling properties and can be advantageously applied to the manufacture of hollow molded articles such as fuel tanks. have.

Description

[0001] The present invention relates to a high density polyethylene copolymer for blow molding,

The present invention relates to a high-density polyethylene copolymer for blow molding, and more particularly to a high-density polyethylene copolymer having excellent die swell characteristics.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, There is a problem that the desired physical properties can not be secured.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single-site catalyst ), A polymer having a narrow molecular weight distribution and a uniform composition distribution of the comonomer is obtained according to the single active site characteristic, and the stereoregularity of the polymer, the copolymerization characteristics, the molecular weight , Crystallinity, and so on.

U.S. Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst supported on each support. However, the amount of the solvent used for preparing the supported catalyst and the preparation time are long , And the metallocene catalyst used had to be carried on the carrier, respectively.

Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution by carrying a double-nucleated metallocene catalyst and a single nuclear metallocene catalyst together with an activating agent in a carrier to change and polymerize the combination of catalysts in the reactor have. However, this method has a limitation in simultaneously realizing the characteristics of the individual catalysts, and also disadvantageously causes fouling in the reactor due to liberation of the metallocene catalyst portion in the carrier component of the finished catalyst.

Accordingly, there is a continuing need for a process for preparing an olefin polymer of desired properties by preparing a hybrid supported metallocene catalyst having excellent activity in order to solve the above-mentioned disadvantages.

On the other hand, the linear low density polyethylene is a resin which is produced by copolymerizing ethylene and an alpha olefin at a low pressure using a polymerization catalyst, has a short molecular weight distribution and a short chain length and has no long chain branch. Linear low density polyethylene film has high tensile strength and elongation as well as general polyethylene characteristics, and has excellent tear strength and falling impact strength. Therefore, it is used for stretch film and overlap film which are difficult to apply low density polyethylene or high density polyethylene .

However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mostly prepared in a single gas phase reactor or a single loop slurry reactor, and productivity is high compared to the process using 1-octene comonomer. Due to limitations of catalyst technology and process technology, there is a problem that the physical properties are considerably weaker than when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability. Much effort has been made to improve these problems,

U.S. Patent No. 4,935,474 discloses a process for preparing polyethylene having a broad molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 discloses a process for producing polyethylene which is excellent in processability using a mixture of a monomer having good comonomer binding property and a monomer having no comonomer binding property and is particularly suitable for a film. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose that a polyethylene having at least two kinds of metal compounds is used as a metallocene-based catalyst and has a molecular weight distribution of at least two, and is used for films, blow molding, It is reported that it is applicable. However, these products have improved processability, but the dispersed state of the unit particles in molecular weight is not uniform, so that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.

In this background, there is a constant demand for the production of a superior product having a balance between physical properties and processability. In particular, polyethylene wafers having a high die swell property and high Mp (molecular weight of maximum peak) It is necessary to prepare the coalescence.

In order to solve the problems of the prior art, the present invention provides a polyethylene copolymer having excellent die swell characteristics and high Mp (molecular weight of maximum peak) value for blow molding.

In order to solve the above problems, the present invention provides an ethylene / alpha-olefin copolymer satisfying the following conditions:

A weight average molecular weight (g / mol) of 200,000 to 300,000,

A molecular weight of maximum peak (Mp) of 50,000 to 150,000,

Wherein the N1 (normal stress) value of the following relational expression 1 is 1.5 or more,

Ethylene / alpha-olefin copolymer:

[Relation 1]

_{N1 (normal stress) = N 1} (first normal stress difference) / SS (shear stress)

In this formula,

N ₁ (first normal stress difference) and SS (shear stress) are measured at 190 ° C with a shear rate of 1 / s, respectively.

The ethylene / alpha-olefin copolymer according to the present invention has physical properties favorable for blow molding. Blow molding is largely an extrusion blow, an injection blow, and an injection blowing method. All of them are made of a hollow pipe (parison or platform), then placed in a mold and blowing air to produce a molded article Process. In this case, when the air is blown, the polymer hollow pipe must be stretched well toward the mold, and the physical properties of the molten state are important so that the shape can not be maintained and sagging phenomenon does not occur. In the present invention, Mp and normal stress values are described below so as to have such physical properties.

The normal stress (N1) means the die swell property of the ethylene / alpha-olefin copolymer. The die swell means an expansion phenomenon in which the polymer resin is swollen and extruded more than the diameter of the die when it passes through a die having a small diameter and is caused by a force generated in a direction perpendicular to the direction of the force applied by the polymer resin .

In the extrusion molding step, if the die swelling property of the polymer is too high, it is difficult to predict the shape of the molded article and the possibility of occurrence of defects increases, which is not preferable. However, in the hollow molding as in the present invention, the polymer hollow pipe must be stretched well toward the mold. In addition, not only the polymer resin must be stretched in the direction of the force to be received but also in the direction perpendicular thereto, The swelling property should be excellent. Particularly, in the case of producing a hollow molded article such as a fuel tank having a wide internal space, die swelling characteristics are considered more importantly.

In the present invention, the ethylene / alpha-olefin copolymer has a high N1 (normal stress) value by controlling the molecular weight and Mp of the ethylene / alpha-olefin copolymer. The die swelling should take into consideration the pressure of the polymer and the pressure applied thereto in the direction perpendicular thereto. In the present invention, the die swell characteristic is evaluated by the N1 (normal stress) value according to the above formula (1). In the relational expression 1, N ₁ (First Normal Stress Difference) and SS (Shear Stress) are respectively measured at 190 ° C. with a shear rate of 1 / s.

The N1 is measured by measuring a shear stress and a normal stress in a direction parallel to the rotation axis by giving a torque to the ethylene / alpha-olefin copolymer and calculating the relationship between the shear stress and the normal stress, (Normal stress) value according to the following equation. Since the value of N1 varies depending on the rotational force and the temperature, in the present invention, the shear rate is 1 / s and the measurement is performed at 190 ° C.

The ethylene / alpha-olefin copolymer according to the present invention has an N1 value of 1.5 or more by the above method. By having the N1 value within the above range, the hollow polymer pipe can be stretched well toward the mold during the hollow molding, so that a hollow molded product having a wide inner space like a fuel tank can be manufactured. Preferably, the N1 value is from 1.5 to 5.

Also, Mp means the molecular weight at the point where the highest peak is obtained when the GPC curve of the ethylene / alpha-olefin copolymer is measured, and the sugar affects the swelling. In particular, the ethylene / alpha-olefin according to the present invention is for producing a hollow molded article such as a fuel tank, and a high Mp value can increase the mechanical properties of the hollow molded article.

The Mp value of the ethylene / alpha-olefin copolymer according to the present invention is 50,000 to 150,000. By having the Mp value in the above range, excellent die swelling characteristics and mechanical properties of the hollow molded article can be improved.

Preferably, the density (g / cm 3) of the ethylene / alpha-olefin copolymer is 0.930 to 0.970, more preferably 0.940 to 0.960.

Preferably, the HLMI of the ethylene / alpha-olefin copolymer is from 1 to 10 g / 10 min, more preferably from 4 to 8 g / 10 min (190 DEG C, melt flow index measured at 21.6 kg load according to ASTM D1238) g / 10 min.

Preferably, the ethylene / alpha-olefin copolymer has a molecular weight distribution (Mw / Mn) of 1 to 20, which shows a broad molecular weight distribution and can exhibit excellent processability.

Specific examples of the alpha-olefin monomers in the ethylene / alpha-olefin copolymer according to the present invention include propylene, 1-butene, 1-pentene, 4-methyl- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like. Preferably, 1-butene may be used as the alpha-olefin monomer.

In the ethylene / alpha-olefin copolymer, the content of the alpha-olefin as the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose and the like of the copolymer. More specifically, it may be more than 0 and 99 mol% or less.

The ethylene / alpha-olefin copolymer may be prepared using a metallocene catalyst. The metallocene catalyst that can be used includes at least one first metallocene compound represented by the following general formula (1): And a compound represented by the following general formula (3) to (5).

[Chemical Formula 1]

In Formula 1,

A is hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -20} aryl, C _{7 -20} alkylaryl, C _{7 -20} aryl, C _{1 -20} alkoxy, C ₂ alkoxy _-20 alkyl, C _{3 -20} heterocycloalkyl, or C _{5 -20} membered heteroaryl;

D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, or C _{6 -20} aryl;

L is C _{1 -10} linear or branched alkylene;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or aryl C _7-20 alkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and each is independently halogen, C _{1 -20} alkyl, C _2-20 alkenyl each other, C _{6 -20} aryl, nitro, amido, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxy, or C _{1 -20} sulfonate;

C ¹ and C ² are the same or different and each independently represents one of the following structural formulas (2a), (2b) or (2c) except that the case where both of C ¹ and C ² are of the general formula (2c);

(2a)

(2b)

[Chemical Formula 2c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to form a substituted or unsubstituted aliphatic or aromatic ring;

(3)

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _{3 -n}

In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _2-20 alkenyl, C _{7 -40} alkylaryl, C _7-40 arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;

Z ¹ is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;

n is 1 or 0;

[Chemical Formula 4]

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _{3 -m}

In Formula 4,

M ² is a Group 4 transition metal;

Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different and are each independently selected from the group consisting of hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _2-20 alkenyl, C _{7 -40} alkylaryl, C _7-40 arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;

Z ² is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;

B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

[Chemical Formula 5]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

In Formula 5,

M ³ is a Group 4 transition metal;

Cp < ⁵ > is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;

R ^e is hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _{2 -20} alkenyl, C _{7 -40} alkylaryl , C _{7 -40} arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;

Z ³ is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;

B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl.

The substituents of the above formulas (1), (3), (4) and (5) will be described more specifically.

Examples of the C _{1 -20} alkyl include linear or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, , But is not limited thereto.

The C _{2 -20} alkenyl includes linear or branched alkenyl, and specifically includes, but is not limited to, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like.

The C _{6 -20} aryl includes aryl of a monocyclic or condensed ring, and specifically includes, but is not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like.

In the C _{5 -20} heteroaryl, it includes monocyclic or condensed polycyclic heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetrahydro Tetrahydropyranyl, tetrahydropyranyl, tetrahydrofuranyl, and the like, but are not limited thereto.

Examples of the C _{1 -20} alkoxy include, but are not limited to, methoxy, ethoxy, phenyloxy, cyclohexyloxy, and the like.

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, and hafnium.

R ₁ to R ₁₇ and R ₁ 'to R ₉ ' in the above formulas (2a), (2b) and (2c) are each independently hydrogen, methyl, ethyl, More preferably, but not limited to, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy or ethoxy.

L in Formula 1 is more preferably C _{4 -8} straight chain or branched alkylene, but is not limited thereto. Further, the alkylene group may be substituted or unsubstituted with C _{1 -20} alkyl, C _{2 -20} alkenyl, or C _{6 -20} aryl.

In the above formula (1), A is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, Tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl, tetrahydrofuranyl or tetrahydrofuranyl.

In addition, B in the above formula (1) is preferably silicon, but it is not limited thereto.

The first metallocene compound of Formula 1 forms a structure in which an indeno indole derivative and / or fluorene derivative is bridged by a bridge, and a non-covalent electron pair which can act as a Lewis base in the ligand structure Thereby supporting the carrier on the surface having Lewis acid properties and exhibiting high polymerization activity even when carried. In addition, the activity is high due to the electron enrichment of the indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and the high activity is maintained even in the presence of hydrogen. Also, it is possible to stabilize the beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding to inhibit beta-hydrogen elimination and polymerize the ultrahigh molecular weight olefin polymer.

According to one embodiment of the present invention, specific examples of the compound represented by the formula (2a) include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, the compound represented by Formula 2b may be a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to one embodiment of the present invention, the compound represented by Formula 2c may be a compound represented by one of the following structural formulas, but the present invention is not limited thereto.

According to an embodiment of the present invention, the first metallocene compound represented by Formula 1 may be a compound represented by one of the following structural formulas, but is not limited thereto.

The first metallocene compound of Formula 1 can polymerize an ethylene / alpha-olefin copolymer having high activity and a high molecular weight. In particular, even when used on a carrier, it exhibits a high polymerization activity, and thus an ethylene / alpha-olefin copolymer having an ultra-high molecular weight can be produced.

Further, even when the polymerization reaction is carried out in the presence of hydrogen to produce an ethylene / alpha-olefin copolymer having a high molecular weight and a broad molecular weight distribution, the first metallocene compound of formula (1) It is possible to polymerize an ultra-high molecular weight ethylene / alpha-olefin copolymer still exhibiting high reactivity. Therefore, even when used in combination with a catalyst having other properties, it is possible to produce an ethylene / alpha-olefin copolymer satisfying the characteristics of high molecular weight without lowering the activity, An ethylene / alpha-olefin copolymer having a broad molecular weight distribution can be easily produced.

The first metallocene compound of Formula 1 is prepared by ligating an indenoindole derivative and / or a fluorene derivative with a bridging compound to prepare a ligand compound, and then adding a metal precursor compound to carry out metallation . The method for producing the first metallocene compound will be described in the following Examples.

The compound represented by Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In the formula (4), when m is 1, it means that a Cp ³ R ^c ring, a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² are bridged by B ¹ , and m is 0 Quot; refers to the structure of the non-crosslinked compound.

The compound represented by Formula 4 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

The compound represented by the formula (5) may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The metallocene catalyst used in the present invention is at least one of the first metallocene compounds represented by the above-mentioned formula (1), and one kind of the second metallocene compound selected from the compounds represented by the above-mentioned formulas (3) to Or more may be carried on a carrier together with a promoter compound.

In addition, the supported metallocene catalyst can induce the formation of LCB (Long Chain Branch) in the ethylene / alpha-olefin copolymer to be produced.

In the supported metallocene catalyst according to the present invention, the co-catalyst to be supported on the support for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and the olefin is polymerized under a general metallocene catalyst It is not particularly limited as long as it can be used in the case of the above.

Specifically, the promoter compound may include at least one of an aluminum-containing primary catalyst of the following general formula (6) and a boron-containing secondary catalyst of the following general formula (7).

[Chemical Formula 6]

_{- [Al (R 18) -O-} ] k -

In Formula (6), R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

(7)

T ⁺ [BG ₄ ] ^-

In formula (7), T ⁺ is a polyvalent ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl And halo-substituted hydrocarbyl, wherein G has 20 or fewer carbons, but G is halide in only one or less positions.

By using such first and second co-catalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and the polymerization activity can be improved.

The first cocatalyst of formula (6) may be an alkylaluminoxane compound having a linear, circular or network-like repeating unit bonded thereto. Specific examples of the first catalyst include methylaluminoxane (MAO), ethylaluminium Isobutylaluminoxane, butylaluminoxane, and the like.

Also, the second cocatalyst of formula (7) may be a tri-substituted ammonium salt, or a dialkylammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium (Tetrafluoroborate) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (Pentafluorophenyl) borate, triphenyl ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluoro Boronate in the form of a tri-substituted ammonium salt such as N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) compound; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis Borate compounds in the form of trisubstituted phosphonium salts such as borate and the like.

In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal to the carrier contained in the first metallocene compound represented by Chemical Formula 1 or the second metallocene compound represented by Chemical Formulas 3 to 5 is 1 : 10 to 1: 1,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape. In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100.

In the supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on its surface can be used as the carrier, and preferably has a hydroxy group and a siloxane group which are dried and have moisture removed from the surface and have high reactivity Can be used.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

On the other hand, the ethylene / alpha-olefin copolymer according to the present invention can be produced by polymerizing ethylene and alpha-olefin in the presence of the above-described supported metallocene catalyst.

The polymerization can be carried out by copolymerizing ethylene and alpha-olefins using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The polymerization temperature may be about 25 to about 500 캜, preferably about 25 to about 200 캜, and more preferably about 50 to about 150 캜. Also, the polymerization pressure may be from about 1 to about 100 Kgf / cm2, preferably from about 1 to about 50 Kgf / cm2, more preferably from about 5 to about 30 Kgf / cm2.

The supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene A chlorine atom-substituted hydrocarbon solvent, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The ethylene / alpha-olefin copolymer according to the present invention can be obtained by using ethylene / alpha-olefin copolymers of the general formula (1), which mainly polymerizes the high molecular weight polymer chains, - olefin monomers. Due to the interaction of these two or more catalysts, a polymer containing a higher content of polymer chains in a high molecular weight region can be obtained while having a broad molecular weight distribution as a whole.

As a result, the ethylene / alpha-olefin copolymer can exhibit, for example, a molecular weight distribution curve as shown in FIG. 1 and can have a high Mp value. Also, as shown in Fig. 2, it has a high Normal Stress value and can be preferably applied to the production of a hollow molded article such as a fuel tank.

The ethylene / alpha-olefin copolymer according to the present invention has a high Mp value and excellent die swelling properties and can be preferably applied to the production of a hollow molded article such as a fuel tank.

Fig. 1 shows the GPC curves of the polymers prepared in the comparative examples and the examples of the present invention.
Fig. 2 shows the results of measurement of normal stress of the polymer prepared in Comparative Examples and Examples of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Manufacturing example  One

Step 1) Preparation of ligand compound

2 g of Fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. (3.6 g) was dissolved in hexane (50 mL), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath. The mixture was stirred overnight at room temperature. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF and 5.5 mL of 2.5 M n-BuLi hexane solution was dissolved in a dry ice / acetone bath And the mixture was stirred at room temperature overnight. dimethyl-5,10-dihydroindeno [1,2-b] indole-2-carboxylic acid was obtained by NMR spectroscopic analysis of the reaction solution of (6- (tert-butoxy) The Li solution was transferred under a dry ice / acetone bath. The mixture was stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water, and the residual water of the organic layer was removed with MgSO ₄ to obtain a ligand compound (Mw = 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were formed.

^{1 H NMR (500 MHz, d} 6 -benzene): -0.30 ~ -0.18 (3H, d), 0.40 (2H, m), 0.65 ~ 1.45 (8H, m), 1.12 (9H, d), 2.36 ~ 2.40 (1H, d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21

Step 2) Preparation of metallocene compound

7.2 g (12 mmol) of the ligand compound synthesized in step 1 above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. And dried in vacuo to obtain a brown color sticky oil. And dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared and 50 mL of toluene was added thereto to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. It was changed to violet color by stirring overnight at room temperature. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to give 6 g of a dark violet metallocene compound as filtered solid (Mw 758.02, 7.92 mmol, yield 66 mol%). Two isomers were observed in < 1 > H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Manufacturing example  2

(CH ₂ ) ₆ -Cl was prepared by the method described in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol, which was reacted with NaCp t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ° C / 0.1 mmHg).

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and then normal butyl lithium (n-BuLi) was slowly added thereto. . The solution was again slowly added at -78 ° C to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 ml) in a suspension solution and slowly added at room temperature Lt; / RTI > for 6 hours.

All volatile materials were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried, and hexane was added thereto to induce a precipitate at a low temperature (-20 ° C). The white solid precipitate was filtered out at a low temperature _{[tBu-O- (CH 2)} 6 -C 5 H 4] 2 ZrCl ₂ to obtain the compound (92% yield).

^{1 H NMR (300 MHz, CDCl} 3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

_{^{13 C NMR (CDCl 3):}} 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Example : Preparation of supported catalyst

Step 1) Carrier drying

Silica (SYLOPOL 948, Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C for 15 hours.

Step 2) Preparation of supported catalyst

Add 10 g of the dried silica of step 1 to a glass reactor, add 100 mL of toluene, and stir. 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was slowly reacted at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After the addition of 100 mL of toluene, 0.25 mmol of the metallocene catalyst prepared in Preparation Example 1 was dissolved in toluene and the mixture was reacted for 1 hour. After the reaction was completed, 0.25 mmol of the metallocene catalyst prepared in Preparation Example 2 was dissolved in toluene, and the reaction was further allowed to proceed for 1 hour. After the reaction was completed, stirring was stopped and the toluene layer was separated and removed. 1.0 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) was added thereto and stirred for 1 hour. Toluene was removed to prepare a supported catalyst.

Comparative Example

10 g of the dried silica of step 1 of the Example was placed in a glass reactor, and 100 mL of toluene was further added thereto and stirred. 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was slowly reacted at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After the addition of 100 mL of toluene, 0.25 mmol of the metallocene catalyst prepared in Preparation Example 2 was dissolved in toluene and the mixture was reacted for 1 hour. After the completion of the reaction, the toluene was removed under reduced pressure at 50 ° C to prepare a supported catalyst.

Experimental Example

Step 1) Ethylene / 1-butene copolymerization

50 mg of each supported catalyst prepared in the above Examples and Comparative Examples were quantitatively measured in a dry box, and each was packed in a 50 mL glass bottle. The packed product was then sealed with a rubber septum and taken out from a dry box to prepare a catalyst to be injected. The polymerization was carried out in a temperature controlled, 2 L metal alloy reactor at high pressure equipped with a mechanical stirrer.

1 L of hexane containing 1.0 mmol of triethylaluminum and 5 mL of 1-butene were charged into the reactor, and the prepared supported catalysts were charged into the reactor without air contact, The monomer was polymerized for 1 hour while continuously feeding at a pressure of 9 Kgf / cm < 2 >. The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation. The polymerization solvent was removed from the obtained polymer by filtration and dried in a vacuum oven at 80 캜 for 4 hours.

Step 2) Evaluation of physical properties of polymer

The polymers prepared in the above Examples and Comparative Examples were evaluated for physical properties by the following methods.

1) Density: ASTM 1505

2) Melt index (MFR, 5 kg / 21.6 kg): Measuring temperature 190 캜, ASTM 1238

3) MFRR _(0.6 MFR ₂₁ / MFR _5): MFR is _0.6 to _21, a melt index (MI, 21.6kg load) divided by the ratio MFR ₅ (MI, 5kg load).

4) Mn, Mw, MWD and GPC curves: Samples were pre-treated in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160 ° C for 10 hours using PL-SP260 and measured using PL-GPC220 The number average molecular weight and the weight average molecular weight were measured at 160 캜. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

5) N1 (normal stress): The polymer is melted at 190 ° C for 5 minutes using ARES (advanced rheometric expansion system, TA instrument) and subjected to a rotational test with shear rate of 0.01 / s to 1 / s It was, and the N ₁ / τ ₁₂ value at shear rate 1 / s to N1.

The results are shown in Table 1 below. The GPC curve of each copolymer is shown in Fig. 1, and the results of N1 (normal stress) measurement are shown in Fig.

unit Comparative Example Example density g / cm3 0.946 0.946 HLMI g / 10 min 7 6 Mp - 46,000 114,000 Mw - 250,000 260,000 MWD - 15.5 15.0 Die Swell % 130 190 N1 - 1.4 1.7

As shown in Table 1 and FIG. 1, it can be seen that the Mp of the Example has shifted to a higher molecular weight than the Comparative Example. In addition, as shown in FIG. 2, it can be seen that the value of N ₁ / τ ₁₂ (N ₁ ) of the embodiment is higher than that of the comparative example as the shear rate increases.

Claims (7)

A weight average molecular weight (g / mol) of 200,000 to 300,000,
A molecular weight of maximum peak (Mp) of 50,000 to 150,000,
Wherein the N1 (normal stress) value of the following relational expression 1 is 1.5 or more,
Ethylene / alpha-olefin copolymer:
[Relation 1]
_{N1 (normal stress) = N 1} (first normal stress difference) / SS (shear stress)
In this formula,
N ₁ (First Normal Stress Difference) and SS (Shear Stress) are respectively measured at 190 ° C with shear rate of 1 / s.
The method according to claim 1,
Wherein the N1 value is from 1.5 to 5. < RTI ID = 0.0 >
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Wherein the ethylene / alpha-olefin copolymer has a density (g / cm < 3 >) of 0.930 to 0.970.
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Characterized in that the HLMI (melt flow index measured at 190 占 폚 under a load of 2.16 kg according to ASTM D1238) is 1 to 10 g / 10 min.
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
Wherein the ethylene / alpha-olefin copolymer has a molecular weight distribution (Mw / Mn) of from 1 to 20,
Ethylene / alpha-olefin copolymer.
The method according to claim 1,
The alpha-olefin is preferably selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Tetradecene, 1-hexadecene, 1-tetradecene, 1-hexadecene, and 1-aidocene.
Ethylene / alpha-olefin copolymer.
The method of claim 1, wherein the ethylene / alpha-olefin copolymer comprises at least one first metallocene compound represented by Formula 1 below: And an ethylene / alpha-olefin copolymer prepared by polymerizing ethylene and an alpha-olefin in the presence of at least one second metallocene compound selected from compounds represented by the following formulas (3) to (5)
[Chemical Formula 1]

In Formula 1,
A is hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -20} aryl, C _{7 -20} alkylaryl, C _{7 -20} aryl, C _{1 -20} alkoxy, C ₂ alkoxy _-20 alkyl, C _{3 -20} heterocycloalkyl, or C _{5 -20} membered heteroaryl;
D is -O-, -S-, -N (R) - or -Si (R) (R ') - , in which R and R' are the same or different from each other, each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, or C _{6 -20} aryl;
L is C _{1 -10} linear or branched alkylene;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or aryl C _7-20 alkyl;
M is a Group 4 transition metal;
X ¹ and X ² are the same or different and each is independently halogen, C _{1 -20} alkyl, C _2-20 alkenyl each other, C _{6 -20} aryl, nitro, amido, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxy, or C _{1 -20} sulfonate;
C ¹ and C ² are the same or different and each independently represents one of the following structural formulas (2a), (2b) or (2c) except that the case where both of C ¹ and C ² are of the general formula (2c);
(2a)

(2b)

[Chemical Formula 2c]

Wherein R ₁ to R ₁₇ and R ₁ 'to R ₉ ' are the same or different from each other and each independently represents hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _7-20 alkyl and aryl, wherein R _At least two adjacent to each other of R ₁₀ to R ₁₇ may be connected to form a substituted or unsubstituted aliphatic or aromatic ring;
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹ _{3 -n}
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _2-20 alkenyl, C _{7 -40} alkylaryl, C _7-40 arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;
Z ¹ is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;
n is 1 or 0;
[Chemical Formula 4]
(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _{3 -m}
In Formula 4,
M ² is a Group 4 transition metal;
Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^c and R ^d are the same or different and are each independently selected from the group consisting of hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _2-20 alkenyl, C _{7 -40} alkylaryl, C _7-40 arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;
Z ² is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;
B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;
m is 1 or 0;
[Chemical Formula 5]
(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂
In Formula 5,
M ³ is a Group 4 transition metal;
Cp < ⁵ > is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;
R ^e is hydrogen, C _{1 -20} alkyl, C _{1 -10} alkoxy, C _{2 -20} alkoxyalkyl, C _{6 -20} aryl, C _{6 -10} aryloxy, C _{2 -20} alkenyl, C _{7 -40} alkylaryl , C _{7 -40} arylalkyl, C _{8 -40} aryl alkenyl, or C _{2 -10} alkynyl;
Z ³ is a halogen atom, C _{1 -20} alkyl, C _{2 -10} alkenyl, C _{7 -40} alkylaryl, C _{7 -40} aryl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene , Substituted or unsubstituted amino, C _{2 -20} alkylalkoxy, or C _{7 -40} arylalkoxy;
B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is C _1-20 alkyl, aryl, substituted alkyl or substituted aryl.

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